CN111944239B - Impact-resistant aging-resistant glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Impact-resistant aging-resistant glass fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an impact-resistant aging-resistant glass fiber reinforced polypropylene composite material which comprises the following components in parts by weight: 1-30 parts of modified load type molecular sieve; 30-50 parts of polypropylene; 15-75 parts of glass fiber; 5-12 parts of compatilizer; 0.1-1.5 parts of antioxidant; 0.1-0.5 part of light stabilizer; the modified load type molecular sieve is a molecular sieve loaded with metal oxide and modified by a silane coupling agent. The invention also provides a preparation method of the glass fiber reinforced polypropylene composite material. According to the invention, the metal oxide is loaded on the molecular sieve, and then the silane coupling agent is used for modification, so that the modified loaded molecular sieve is added into the glass fiber reinforced polypropylene composite material, the impact resistance and ageing resistance of the composite material can be improved, and the cost of the composite material is reduced.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polypropylene composite material and a preparation method thereof.
Background
The nonmetal high polymer material, most common traditional plastics such as polyethylene, polypropylene, nylon and the like are widely applied to our life, and the plastic products after glass fiber reinforcement have higher tensile strength, bending strength and shock resistance than the common plastics, and the density of the nonmetal high polymer material is also greatly lower than that of metal, so that the nonmetal high polymer material is an ideal material for realizing light weight.
However, with the continuous expansion of application scenes, the requirements on the mechanical properties and ageing resistance of the glass fiber reinforced polypropylene composite material are also higher and higher. The glass fiber reinforced polypropylene composite material can improve the mechanical property to a certain extent by adding powder fillers such as talcum powder, calcium carbonate and the like, but still has difficulty in meeting the application scene with high requirement on the mechanical property. In addition, in order to prolong the service life of the glass fiber reinforced polypropylene composite material, the conventional method is to add ultraviolet light absorbers or light stabilizers, such as benzophenones, benzotriazoles, salicylates and the like, but in actual use, the ultraviolet light resistance effect is not outstanding, the ultraviolet light resistance effect or decomposition products thereof have certain toxicity, the environment is not protected, and the use of the organic light stabilizers also increases the cost of the composite material.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the background art, and provides a glass fiber reinforced polypropylene composite material with excellent shock resistance and ageing resistance and a preparation method thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an impact-resistant and aging-resistant glass fiber reinforced polypropylene composite material comprises the following components in parts by weight:
the modified load type molecular sieve is a molecular sieve loaded with metal oxide and modified by a silane coupling agent.
In the glass fiber reinforced polypropylene composite material, preferably, the molecular sieve is a zeolite molecular sieve with the aperture of 0.3-50 nanometers and treated by nitric acid, and the zeolite molecular sieve comprises one or more of MCM-22, ZSM-5, mordenite molecular sieve, Y-type molecular sieve, 13X molecular sieve and MCM-41.
In the glass fiber reinforced polypropylene composite material, preferably, the metal oxide includes one or more of zinc oxide, iron oxide, cerium oxide and titanium dioxide.
In the glass fiber reinforced polypropylene composite material, preferably, the silane coupling agent comprises one or more of methyltrimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, gamma-aminopropyl triethoxysilane and gamma- (2, 3-glycidoxy) propyl trimethoxysilane.
In the glass fiber reinforced polypropylene composite material, preferably, the modified supported molecular sieve is prepared by firstly pretreating the molecular sieve with nitric acid, then supporting the molecular sieve treated with nitric acid with metal oxide, and then modifying the molecular sieve with a silane coupling agent.
In the glass fiber reinforced polypropylene composite material, the pretreatment of the molecular sieve by nitric acid preferably comprises the following steps: preparing 1-2mol/L nitric acid solution, adding molecular sieve into the nitric acid solution, stirring at 60-90 ℃ for 4-8h, filtering, taking out the filter cake, drying, and calcining at 500-650 ℃ for 5-10h.
In the glass fiber reinforced polypropylene composite material, preferably, the nitric acid treated molecular sieve supported metal oxide comprises the following steps: preparing an oxide precursor into a 0.5-2.0mol/L aqueous solution, uniformly mixing a molecular sieve subjected to nitric acid treatment with the precursor aqueous solution, stirring for 5-8 hours at 60-90 ℃, filtering to obtain a filter cake, repeating the above processes for a plurality of times (2-5 times), drying the filter cake at 110 ℃ for 6-12 hours after the last filtering, and calcining at 500-650 ℃ for 5-10 hours after drying; the oxide precursor comprises one or more of nitrate-type precursor, acetate-type precursor, sulfate-type precursor and chloride-type precursor.
In the glass fiber reinforced polypropylene composite material, preferably, the modification with the silane coupling agent comprises the following steps: and (3) dropwise adding the silane coupling agent solution into the molecular sieve loaded with the metal oxide, and then carrying out reflux reaction for 8-14h at 120-140 ℃.
In the glass fiber reinforced polypropylene composite material, preferably, the polypropylene is one or a mixture of a plurality of homo-polypropylene, co-polypropylene and random co-polypropylene, and the solution flow rate of the polypropylene under the condition of 2.16kg/230 ℃ is 5-100g/min. The glass fibers are continuous glass fibers, the linear density is 1000-2400tex, and the diameter of each glass fiber is 10-30 microns. The compatilizer is maleic anhydride grafted polypropylene, and the grafting rate of the polypropylene is 0.5-2.5wt%. The antioxidant is one or more of tris [2, 4-di-tert-butylphenyl ] phosphite antioxidants and hindered phenol antioxidants. The light stabilizer is one or more of benzophenones, benzotriazoles, salicylates or triazines.
The invention also provides a preparation method of the glass fiber reinforced polypropylene composite material, which comprises the following steps:
(1) Mixing the modified load type molecular sieve, polypropylene, a compatilizer, an antioxidant and a light stabilizer, adding the mixture into a double-screw extruder, and extruding the mixture into a melt tank through the double-screw extruder;
(2) Making the continuous glass fiber enter a melt tank for impregnation treatment, and then pressing to prepare a continuous glass fiber unidirectional prepreg tape;
(3) And layering and stacking the continuous glass fiber unidirectional prepreg tapes according to the fiber directions of 0 degrees and 90 degrees, and performing hot pressing and exhausting to obtain the glass fiber reinforced polypropylene composite material.
In the above preparation method, preferably, the technological parameters of the twin-screw extruder are controlled as follows: the first area temperature is 160-195 ℃, the second area temperature is 170-200 ℃, the third area temperature is 180-220 ℃, the fourth area temperature is 200-210 ℃, the fifth area temperature is 200-220 ℃, the melt temperature is 200-220 ℃, the machine head temperature is 210-225 ℃ and the melt tank temperature is 200-230 ℃.
The invention provides a glass fiber reinforced polypropylene composite material modified by a molecular sieve loaded with metal oxide and a preparation method thereof, which further improve the shock resistance and ageing resistance of the composite material, so that the composite material can be widely applied to the fields of rail transit equipment and rail engineering construction.
According to the invention, the metal oxide is loaded into the molecular sieve after nitric acid treatment, and then the molecular sieve is subjected to silanization modification and then doped into the glass fiber reinforced polypropylene composite material, so that the mechanical property of the glass fiber reinforced polypropylene composite material can be improved, and the glass fiber reinforced polypropylene composite material has higher impact strength. The addition of the molecular sieve can change the crystallization behavior of pure polypropylene due to the large specific surface area and small crystal grain, reduce the defects in the polypropylene matrix, and can interact with the polymer chains of the polymer to stabilize the molecular chains and prevent the molecular chains from sliding, so that the impact resistance of the product can be improved as a whole. After the molecular sieve is modified by the silane coupling agent, compared with the unmodified molecular sieve, the dispersibility of the molecular sieve in the polypropylene matrix is improved, the interfacial bonding strength between the molecular sieve and the polypropylene matrix is improved, and the interaction force of two phases is enhanced, so that the mechanical properties of the composite material are further improved.
The molecular sieve is a porous material, has a regular crystal structure and a highly ordered pore canal system, has a large specific surface area and strong adsorption capacity, and the pore canal size can be regulated and controlled between 0.3 and 50 nanometers by a specific method. The research shows that the mechanical property of the glass fiber reinforced polypropylene composite material can be improved by loading the metal oxide into the molecular sieve and then adding the metal oxide into the glass fiber reinforced polypropylene composite material, but the stability, the dispersion performance and the like of the metal oxide are difficult to ensure when the metal oxide is loaded onto the molecular sieve, and the final modification effect is also difficult to ensure. According to the invention, the molecular sieve is subjected to nitric acid treatment, and the connecting channels among different pore channel systems are opened, so that the pore channels of the molecular sieve are distributed in multiple stages, the molecular sieve distributed in multiple stages can stabilize metal oxides with different particle sizes, and the metal oxides with different particle sizes can be stably and uniformly present in the pore channels of the molecular sieve, so that the metal oxides are not easy to fall off. In addition, after the metal oxide is loaded on the molecular sieve subjected to nitric acid treatment, the metal oxides with different particle sizes can stably exist in different pore channel structures of the molecular sieve, and agglomeration among the metal oxides can be reduced.
According to the invention, the metal oxide is stably present along with the multistage distribution of the molecular sieve pore channels, so that the use amount of the ultraviolet light absorber or the light stabilizer is greatly reduced, the ageing resistance of the glass fiber reinforced polypropylene composite material is improved, and the production cost is reduced.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the metal oxide is loaded on the molecular sieve, and then the silane coupling agent is used for modification, so that the modified loaded molecular sieve is added into the glass fiber reinforced polypropylene composite material, the impact resistance and ageing resistance of the composite material can be improved, and the cost of the composite material is reduced.
2. The preparation method of the glass fiber reinforced polypropylene composite material is simple and feasible, is suitable for industrial production, and can be widely applied to the fields of rail transit equipment and rail engineering construction.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of protection of the present invention is not limited to the specific embodiments described below.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
an impact-resistant and aging-resistant glass fiber reinforced polypropylene composite material comprises the following components in parts by weight:
the modified supported molecular sieve is a molecular sieve which is supported with metal oxide and modified by a silane coupling agent. Specifically, the modified supported molecular sieve is prepared by firstly pretreating the molecular sieve with nitric acid, loading metal oxide on the molecular sieve after nitric acid treatment, and modifying the molecular sieve with a silane coupling agent, wherein the metal oxide is zinc oxide, the molecular sieve is a ZSM-5 molecular sieve, and the silane coupling agent is gamma-aminopropyl triethoxysilane (KH 550).
In this example, a ZSM-5 molecular sieve treated with nitric acid comprises the steps of: nitric acid is prepared into a solution of 1.0mol/L, then ZSM-5 molecular sieve is added into the nitric acid solution (solid-to-liquid ratio is 1g molecular sieve/20 ml nitric acid solution), stirring is carried out for 4 hours at 80 ℃, then filtering is carried out, filter cakes are taken out in a baking oven at 110 ℃ for drying for 5 hours, and calcination is carried out at 600 ℃ for 5 hours.
In this example, the molecular sieve supported metal oxide treated with nitric acid comprises the steps of: preparing zinc acetate into 0.8mol/L aqueous solution, uniformly mixing a ZSM-5 molecular sieve modified by nitric acid with the zinc acetate aqueous solution, stirring for 6 hours at 80 ℃, filtering to obtain a filter cake, repeating the process for 3 times, taking the filter cake out of a 110 ℃ oven after the last filtering, drying for 8 hours, and calcining for 10 hours at 600 ℃.
In this example, the modification with the silane coupling agent includes the steps of: the toluene solution of the silane coupling agent KH550 is dripped into the molecular sieve loaded with the metal oxide, and then the mixture is refluxed at 120 ℃ for 10 hours, washed and dried.
In this example, the polypropylene was a copolymer polypropylene having a melt flow rate of 40g/10min and a test condition of 230℃at 2.16kg; the glass fiber is continuous alkali-free glass fiber, the fiber diameter is 17 micrometers, and the linear density is 1200tex; the compatilizer is maleic anhydride grafted polypropylene, the grafting rate is 1.0%, the melt flow rate is 100g/10min, and the test condition is 230 ℃ and 2.16kg; the antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite, namely antioxidant 168; the light stabilizer is 2-hydroxy-4-n-octoxybenzophenone, namely ultraviolet absorber UV531.
The preparation method of the glass fiber reinforced polypropylene composite material comprises the following steps:
(1) Sequentially adding the modified load type molecular sieve, polypropylene, a compatilizer, an antioxidant and a light stabilizer into a high-speed mixer, mixing for 5min, adding into a hopper of a double-screw extruder, and extruding into a melt tank through the double-screw extruder; the technological parameters of the twin-screw extruder are controlled as follows: the temperature of the first area is 180 ℃, the temperature of the second area is 190 ℃, the temperature of the third area is 205 ℃, the temperature of the fourth area is 210 ℃, the temperature of the fifth area is 215 ℃, the temperature of the melt is 215 ℃, the temperature of the machine head is 215 ℃, the temperature of the melt tank is 220 ℃, and the rotating speed is 500 revolutions per minute;
(2) Spreading and preheating the continuous glass fibers to obtain preheated continuous glass fibers;
(3) Introducing glass fiber into one side of a melt tank, introducing glass fiber into the other side of the melt tank, wherein the traction speed of the glass fiber is 1-80 m/min, and pressing by a press to obtain a continuous glass fiber unidirectional prepreg tape with the thickness of 0.15-0.35 mm;
(4) And layering and stacking the continuous glass fiber unidirectional prepreg tapes according to the fiber directions of 0 degrees and 90 degrees, and performing hot pressing and exhausting to obtain the glass fiber reinforced polypropylene composite material.
Example 2:
an impact-resistant and aging-resistant glass fiber reinforced polypropylene composite material comprises the following components in parts by weight:
the modified supported molecular sieve is a molecular sieve which is supported with metal oxide and modified by a silane coupling agent. Specifically, the modified supported molecular sieve is prepared by firstly pretreating the molecular sieve with nitric acid, loading metal oxide on the molecular sieve after nitric acid treatment, and modifying the molecular sieve with a silane coupling agent, wherein the metal oxide is ferric oxide, the molecular sieve is MCM-22 molecular sieve, and the silane coupling agent is gamma-aminopropyl triethoxysilane (KH 550).
In this example, an MCM-22 molecular sieve treated with nitric acid includes the steps of: nitric acid is prepared into a solution of 1.0mol/L, then MCM-22 molecular sieve is added into nitric acid solution (solid-to-liquid ratio is 1g molecular sieve/20 ml nitric acid solution), stirring is carried out for 4 hours at 80 ℃, then filtering is carried out, filter cakes are taken out in a baking oven at 110 ℃ for 5 hours, and calcination is carried out at 600 ℃ for 5 hours after drying.
In this example, the molecular sieve supported metal oxide treated with nitric acid comprises the steps of: preparing ferric nitrate into 1.2mol/L aqueous solution, uniformly mixing the MCM-22 molecular sieve modified by nitric acid with the aqueous solution of ferric nitrate, stirring for 8 hours at 70 ℃, filtering to obtain a filter cake, repeating the above process for 3 times, taking the filter cake out of a 110 ℃ oven after the last filtering, drying for 10 hours, and calcining for 9 hours at 550 ℃.
In this example, the modification with the silane coupling agent includes the steps of: the toluene solution of the silane coupling agent KH550 is dripped into the molecular sieve loaded with the metal oxide, and then the mixture is refluxed at 120 ℃ for 10 hours, washed and dried.
In this example, the polypropylene was a copolymer polypropylene having a melt flow rate of 40g/10min and a test condition of 230℃at 2.16kg; the glass fiber is continuous alkali-free glass fiber, the fiber diameter is 17 micrometers, and the linear density is 1200tex; the compatilizer is maleic anhydride grafted polypropylene, the grafting rate is 1.0%, the melt flow rate is 100g/10min, and the test condition is 230 ℃ and 2.16kg; the antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite, namely antioxidant 168; the light stabilizer is 2-hydroxy-4-n-octoxybenzophenone, namely ultraviolet absorber UV531.
The preparation method of the glass fiber reinforced polypropylene composite material comprises the following steps:
(1) Sequentially adding the modified load type molecular sieve, polypropylene, a compatilizer, an antioxidant and a light stabilizer into a high-speed mixer, mixing for 5min, adding into a hopper of a double-screw extruder, and extruding into a melt tank through the double-screw extruder; the technological parameters of the twin-screw extruder are controlled as follows: the temperature of the first area is 180 ℃, the temperature of the second area is 190 ℃, the temperature of the third area is 210 ℃, the temperature of the fourth area is 210 ℃, the temperature of the fifth area is 215 ℃, the temperature of the melt is 215 ℃, the temperature of the machine head is 215 ℃, the temperature of the melt tank is 220 ℃, and the rotating speed is 500 revolutions per minute;
(2) Spreading and preheating the continuous glass fibers to obtain preheated continuous glass fibers;
(3) Introducing glass fiber into one side of a melt tank, introducing glass fiber into the other side of the melt tank, wherein the traction speed of the glass fiber is 1-80 m/min, and pressing by a press to obtain a continuous glass fiber unidirectional prepreg tape with the thickness of 0.15-0.35 mm;
(4) And layering and stacking the continuous glass fiber unidirectional prepreg tapes according to the fiber directions of 0 degrees and 90 degrees, and performing hot pressing and exhausting to obtain the glass fiber reinforced polypropylene composite material.
Example 3:
an impact-resistant and aging-resistant glass fiber reinforced polypropylene composite material comprises the following components in parts by weight:
the modified supported molecular sieve is a molecular sieve which is supported with metal oxide and modified by a silane coupling agent. Specifically, the modified supported molecular sieve is prepared by pretreating the molecular sieve with nitric acid, loading metal oxide on the molecular sieve after nitric acid treatment, and modifying with a silane coupling agent, wherein the metal oxide is cerium oxide, the molecular sieve is mordenite molecular sieve, and the silane coupling agent is gamma-aminopropyl triethoxysilane (KH 550).
In this example, a mordenite molecular sieve treated with nitric acid comprises the steps of: nitric acid is prepared into a solution of 1.0mol/L, then mordenite molecular sieve is added into the nitric acid solution (solid-to-liquid ratio is 1g molecular sieve/20 ml nitric acid solution), stirring is carried out for 4 hours at 80 ℃, then filtering is carried out, filter cakes are taken out in a baking oven at 110 ℃ for 5 hours, and calcination is carried out at 600 ℃ for 5 hours after drying.
In this example, the molecular sieve supported metal oxide treated with nitric acid comprises the steps of: preparing cerium oxide into 1.0mol/L aqueous solution, uniformly mixing a mordenite molecular sieve modified by nitric acid with the cerium oxide aqueous solution, stirring for 6 hours at 80 ℃, filtering to obtain a filter cake, repeating the process for 3 times, taking the filter cake out of a 110 ℃ oven after the last filtering, drying for 10 hours, and calcining for 10 hours at 580 ℃.
In this example, the modification with the silane coupling agent includes the steps of: the toluene solution of the silane coupling agent KH550 is dripped into the molecular sieve loaded with the metal oxide, and then the mixture is refluxed at 120 ℃ for 10 hours, washed and dried.
In this example, the polypropylene was a copolymer polypropylene having a melt flow rate of 40g/10min and a test condition of 230℃at 2.16kg; the glass fiber is continuous alkali-free glass fiber, the fiber diameter is 17 micrometers, and the linear density is 1200tex; the compatilizer is maleic anhydride grafted polypropylene, the grafting rate is 1.0%, the melt flow rate is 100g/10min, and the test condition is 230 ℃ and 2.16kg; the antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite, namely antioxidant 168; the light stabilizer is 2-hydroxy-4-n-octoxybenzophenone, namely ultraviolet absorber UV531.
The preparation method of the glass fiber reinforced polypropylene composite material comprises the following steps:
(1) Sequentially adding the modified load type molecular sieve, polypropylene, a compatilizer, an antioxidant and a light stabilizer into a high-speed mixer, mixing for 5min, adding into a hopper of a double-screw extruder, and extruding into a melt tank through the double-screw extruder; the technological parameters of the twin-screw extruder are controlled as follows: the temperature of the first area is 180 ℃, the temperature of the second area is 190 ℃, the temperature of the third area is 205 ℃, the temperature of the fourth area is 205 ℃, the temperature of the fifth area is 215 ℃, the temperature of the melt is 215 ℃, the temperature of the machine head is 215 ℃, the temperature of the melt tank is 220 ℃, and the rotating speed is 500 revolutions per minute;
(2) Spreading and preheating the continuous glass fibers to obtain preheated continuous glass fibers;
(3) Introducing glass fiber into one side of a melt tank, introducing glass fiber into the other side of the melt tank, wherein the traction speed of the glass fiber is 1-80 m/min, and pressing by a press to obtain a continuous glass fiber unidirectional prepreg tape with the thickness of 0.15-0.35 mm;
(4) And layering and stacking the continuous glass fiber unidirectional prepreg tapes according to the fiber directions of 0 degrees and 90 degrees, and performing hot pressing and exhausting to obtain the glass fiber reinforced polypropylene composite material.
Comparative example 1:
this comparative example is different from example 1 in that zinc oxide was not supported on the nitric acid-treated ZSM-5 molecular sieve, and the other conditions were the same as in example 1.
Comparative example 2:
this comparative example is compared to example 2, except that no iron oxide is supported on the nitric acid treated MCM-22 molecular sieve, with the remaining conditions being the same as example 2.
Comparative example 3:
this comparative example is compared to example 3 except that no cerium oxide was supported on the mordenite molecular sieve treated with nitric acid, and the remaining conditions were the same as in example 3.
Comparative example 4:
the glass fiber reinforced polypropylene composite material comprises the following components in parts by weight:
the inorganic filler is calcium carbonate, a modified load type molecular sieve is not adopted, and other components and preparation methods are the same as those of the embodiment.
Comparative example 5:
this comparative example is different from example 1 in that the ZSM-5 molecular sieve was not subjected to nitric acid treatment, but zinc oxide was supported on the ZSM-5 molecular sieve not subjected to nitric acid treatment, and the other conditions were the same as example 1.
The performance test characterization was performed on examples 1-3 and comparative examples 1-5, with the results shown in Table 1 below:
table 1: results of Performance test conducted in examples 1-3 and comparative examples 1-5
In the above table, the performance test criteria are as follows:
testing of tensile Properties: GB/T1447-2005 method for testing tensile Properties of fiber-reinforced plastics.
Test of bending properties: GB/T1449-2005 method for testing bending Property of fiber-reinforced plastics.
Notched impact strength test: GB/T1451-2005 method for testing the impact toughness of fiber reinforced plastics with simple beam.
Ultraviolet light resistance test: GB/T16422.3-2014 Plastic laboratory light Source Exposure test method part 3: fluorescent ultraviolet lamp.
As can be seen from the test results of examples 1-3 and comparative examples 1-5, the glass fiber reinforced polypropylene composite materials of examples 1-3 were subjected to ultraviolet aging test, and the mechanical properties were significantly lower than those of the glass fiber reinforced polypropylene composite materials doped with the molecular sieve without the metal oxide added in comparative examples 1-3, and the glass fiber reinforced polypropylene composite materials without the silane coupling agent modified supported molecular sieve but with increased amounts of antioxidant and light stabilizer added in comparative example 4. Meanwhile, the initial mechanical properties in comparative example 5 are higher, but the properties are obviously reduced after aging test, which also shows that the multistage pore canal formed by the molecular sieve treated by acid plays an important role in improving the stability of the metal oxide. The result proves that the durability of the glass fiber reinforced polypropylene composite material prepared by the invention can be greatly improved, and the long-term outdoor use is satisfied.
Claims (6)
1. The impact-resistant aging-resistant glass fiber reinforced polypropylene composite material is characterized by comprising the following components in parts by weight:
1-30 parts of modified load type molecular sieve;
30-50 parts of polypropylene;
15-75 parts of glass fiber;
5-12 parts of compatilizer;
0.1-1.5 parts of antioxidant;
0.1-0.5 part of light stabilizer;
the modified load type molecular sieve is a molecular sieve loaded with metal oxide and modified by a silane coupling agent;
the molecular sieve is a zeolite molecular sieve with the aperture of 0.3-50 nanometers and treated by nitric acid, and the zeolite molecular sieve comprises one or more of MCM-22, ZSM-5, mordenite molecular sieve, Y-type molecular sieve, 13X molecular sieve and MCM-41;
the modified load type molecular sieve is characterized in that firstly nitric acid is utilized to pretreat the molecular sieve, then the molecular sieve subjected to nitric acid treatment is loaded with metal oxide, and then silane coupling agent is utilized to modify the molecular sieve;
the pretreatment of the molecular sieve with nitric acid comprises the following steps: preparing 1-2mol/L nitric acid solution, adding a molecular sieve into the nitric acid solution, stirring for 4-8 hours at 60-90 ℃, filtering, taking out a filter cake, drying, and calcining for 5-10 hours at 500-650 ℃;
the molecular sieve supported metal oxide treated with nitric acid comprises the following steps: preparing an oxide precursor into 0.5-2.0mol/L aqueous solution, uniformly mixing a molecular sieve subjected to nitric acid treatment with the precursor aqueous solution, stirring at 60-90 ℃ for 5-8 hours, filtering to obtain a filter cake, repeating the above processes for a plurality of times, taking out the filter cake after the last filtering, drying, and calcining at 500-650 ℃ for 5-10 hours; the oxide precursor comprises one or more of nitrate-type precursor, acetate-type precursor, sulfate-type precursor and chloride-type precursor.
2. The glass fiber reinforced polypropylene composite of claim 1, wherein the metal oxide comprises one or more of zinc oxide, iron oxide, cerium oxide, and titanium dioxide.
3. The glass fiber reinforced polypropylene composite of claim 1, wherein the silane coupling agent comprises one or more of methyltrimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, γ -aminopropyl triethoxysilane, and γ - (2, 3-epoxypropoxy) propyl trimethoxysilane.
4. The glass fiber reinforced polypropylene composite of claim 1, wherein the modification with a silane coupling agent comprises the steps of: and (3) dropwise adding the silane coupling agent solution into the molecular sieve loaded with the metal oxide, and then carrying out reflux reaction for 8-14h at 120-140 ℃.
5. A method for preparing a glass fiber reinforced polypropylene composite material according to any one of claims 1 to 4, comprising the steps of:
(1) Mixing the modified load type molecular sieve, polypropylene, a compatilizer, an antioxidant and a light stabilizer, adding the mixture into a double-screw extruder, and extruding the mixture into a melt tank through the double-screw extruder;
(2) Making the continuous glass fiber enter a melt tank for impregnation treatment, and then pressing to prepare a continuous glass fiber unidirectional prepreg tape;
(3) And layering and stacking the continuous glass fiber unidirectional prepreg tapes according to the fiber directions of 0 degrees and 90 degrees, and performing hot pressing and exhausting to obtain the glass fiber reinforced polypropylene composite material.
6. The method according to claim 5, wherein the technological parameters of the twin-screw extruder are controlled as follows: the first area temperature is 160-195 ℃, the second area temperature is 170-200 ℃, the third area temperature is 180-220 ℃, the fourth area temperature is 200-210 ℃, the fifth area temperature is 200-220 ℃, the melt temperature is 200-220 ℃, the machine head temperature is 210-225 ℃ and the melt tank temperature is 200-230 ℃.
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